Multitudinous natural and synthetic polymers are comprised, as important integral parts of at least portions of their constitution(s), of an essential amidocarbonylic moiety or unit of the Structure: ##STR1##
The Structure (A) unit is found either as a segment of a substituent extending from the polymer chain or "backbone" part of the chain continuation in the polymer or as a direct linear inclusion in the polymer backbone, per se. Illustrative of polymeric structures in which the amidocarbonylic unit is in and forms part of the chain itself are the various proteins, such as albumin, and peptides as well as synthetic proteins and the nylon-types of synthetic polymers. See, in this connection, References Numbers (i.e., "Refs. Nos.") 1,2 and 13 in the hereto appendixed LISTING OF REFERENCES Section of the instant Specification. The first-mentioned sort of substituent amidocarbonylic unit inclusion appear in the so-called pyrrolidone, cyclic carbamate and oxazoline WSP's as are well-exemplified in Refs. Nos. 5, 6, 8-12, 14-21, 24, 27 and 28.
Of particular interest and characterization are WSP materials of the following Formulae (I) and (II).
The structural representation of the Formula (I) polymers which encompasses their presently-contemplated breadth and scope (as produced from the monomeric precursors thereof) is: ##STR2## D is selected from the group consisting of oxygen (i.e., "O"), amino (i.e., "--NH--"), methylene (i.e., "--CH.sub.2 --"), alkyl-substituted methylenes (i.e., "--CHR--", in which R contains from 1 to about 3 carbon atoms as in methyl, ethyl, propyl and isopropyl), ##STR3## all of which are obvious divalent groupings; E is a divalent group which, in every occurrence and regardless of specific entity, introduces and provides either two or three carbon (i.e., "C") atoms at and in the indicated heterocyclic ring site between the nitrogen (i.e., "N") atom and the divalent D grouping therein and thereof and which is a moiety or unit representable by the Structure: EQU --(CHR').sub.x, (B)
in which x is an integer with a value of 2 or 3 and R' is hydrogen (i.e., "H") in both or all three of the interconnected Structure (B) units with the exception that in any one of them R' can be, alternatively and additionally to H in a single given instance, a substituent selected from the group consisting of hydroxyl, alkyl units containing from 1 to about 30 carbon atoms therein, hydroxyalkyl units containing the same possible number(s) of carbon atoms therein as said alkyl units (which is the applicable case for all other substituted alkyl groups here specified), phenylalkyl units, halophenylalkyl units, cycloalkyl units containing either 5 or 6 carbon atoms, alkyl-substituted 5 or 6 carbon cycloalkyl units, halogenated alkyl-substituted 5 or 6 carbon cycloalkyl units, haloalkyl units, phenyl units, alkyl-substituted phenyl units, halophenyl units, alpha-naphthyl and beta-naphthyl units and halogenated and/or alkyl-substituted alpha- and/or beta-naphthyls; and
L is selected from the group consisting of vinyl, allyl or isopropenyl which, by known addition polymerizations thereof, respectively become moieties of the respective Structures: ##STR4## in which y is a plural integer which can have a value as high as 5,000 or even more excepting in the instances when the Formula (I) compound is monomeric wherein the value of y is 1 and the L Structures are, respectively: ##STR5##
Representative of groupings symbolized by E in the above Formula (I) are: ethylene (or dimethylene); hydroxyethylene; trimethylene; methylethylene (or isopropylene); hydroxymethylene; 1,2-dimethylethylene (or 2,3-n-butylene); 1,3-amylene; 2,3-amylene; 2,4-amylene; 1,2-hexylene; 2,3-hexylene; 2,4-hexylene; 3,4-hexylene; cyclohexyl ethylene; 3-cyclohexyl-1,2-propylene; 1-cyclohexyl-1,2-butylene; 1-cyclohexyl-1,3-butylene; 1-cyclohexyl-2,3-butylene; 2-cyclohexyl-1,2-butylene; 2-cyclohexyl-1,3-butylene; cyclobutylene; 3-cyclobutyl-1,2-propylene; 1-cyclobutyl-1,2-butylene; 1-cyclobutyl-1,3-butylene; 1-cyclobutyl-2,3-butylene; 2-cyclobutyl-1,2-butylene; 2-cyclobutyl-1,3-butylene; phenylethylene; 1-phenyl-1,3-propylene; 1-phenyl-1,2-propylene; 1,3-diphenyl-1,2-propylene; 2-phenyl-1,3-propylene; (1-p-chlorophenyl)trimethylene; 2(2,4,5-trichlorophenyl)-3,4-hexylene; 1-(p-chlorophenyl)trimethylene; 1-(p-fluorophenyl)trimethylene; 1-(p-bromophenyl)trimethylene; 1-(p-iodophenyl)trimethylene; 2-(2,4,5-trichlorophenyl)-3,4-hexamethylene; 2-(2,4,5-trifluorophenyl)-3,4-hexamethylene; 2-(2,4,5-tribromophenyl)-3,4-hexamethylene; 2-(2,4,5-triiodophenyl)-3,4-hexamethylene; (p-tolyl)ethylene; 2-(o-tolyl)-1,3-trimethylene; alphanaphthylethylene; 1-beta-naphthyl-1,3-trimethylene; 1,2-phenylene; 4-chloro-1,2-phenylene; 1-fluoro-1,2-phenylene; 4-bromo-1,2-phenylene; 4-iodo-1,2-phenylene; and so forth with other like(s) and equivalent(s).
More precisely illustrative (but by no means limiting) of the heterocyclic entities which are includable in the Formula (I) materials of either monomeric or polymeric nature are those of the Structures: ##STR6##
As indicated, polymers of Formula (I) materials usually contain a considerable plurality of interpolymerized repetitive units in their structure. To elucidate this using PVP as an example, the data in the following TABLE I is illustrative, wherein the K-value (according to Fikentscher) is given along with the number average molecular weight (i.e., "M.sub.n ") and the value of y in Structure (C) for each sample therein included.
TABLE I ______________________________________ MOLECULAR PROPERTIES OF VARIOUS PVP PRODUCTS K-value M.sub.n y ______________________________________ 15 10,000 90 30 40,000 360 60 160,000 1440 90 360,000 3240 ______________________________________
This is at least approximately representative, taking into account specific molecular weight differences and other varying factors involved in the diverse species possible to embody, of other polymeric products of the formula (I); the same being in more-or-less approximate correspondence to the below-defined Formula (II) oxazoline polymeric products. While the K-values of the various contemplated WSP's can vary from about 2 to about 200, those having such values in excess of about 90 or so are sometimes relatively unattractively difficult to handle and employ insofar as concerns practical working and applicability purposes. Most frequently, WSP's having K-values in the neighborhood of 30 are most advantageous and desirable, taking all things into account, for utilization. On the other hand, certain varieties of cross-linked WSP's in which, in practical effect, there is an infinite (or at least realistically unmeasurable) molecular weight can sometimes find desirable utilization. While strictly speaking, such cross-linked products are almost invariably water-insoluble or of extremely limited aqueous solubility potential on an order approaching vanishing point dissolution capability in water, they can be and are considered WSP's within the frame of reference of the present contemplation. A good example of such a commercially-available water insoluble PVP is POLYCLAR-AT (Reg. TM) from GAF CORP.
Of the Formula (I) polymers ordinarily selected for employment, PVP and PVO-M are frequently favorite for reasons of good performance qualities and/or availability.
The solubility characteristics of PVP and PVO-M are interesting and of significance for various applicabilities. As is the case for molecular properties, the solubility features of both of these WSP's, while not strictly correlative in any general sense, are to lesser-or-greater degrees indicative of what can be expectable with at least the preponderance of the other possible Formulae (I) and (II) polymeric products.
While, expecting for cross-linked variations, PVP is generally soluble in water at literally all concentration and temperature levels, PVO-M has a peculiar and oftentimes valuable characteristic of inverse solubility with increasing water temperature. Thus, a K-30 PVO-M is generally soluble in water at 25.degree. C. in literally all concentrations, especially in the range of 10 to 50 percent by weight (i.e., "wt.%"), based on total solution weight of the dissolved polymer. On the other hand, PVO-M is insoluble in water, especially in the same 10-50 wt.% range, when the temperature is 50.degree. C. Aqueous solutions of PVO-M tend to become "cloudy" at the 37.degree.-40.degree. C. level with the polymer actually coming out of solution as a stickly mass at about 40.degree. C. In other words, the "Cloud Point" of PVO-M in water is about 37.degree. C.
By way of further illustration, the general solubilities of a K-30 PVO-M and a K-29-32 PVP in various alcohols, glycols, alkanolamines, acids, diamines, chlorinated hydrocarbons, aldehydes and other random solvent compounds when observed in about 0.5 wt.% concentrations under cool to hot conditions is observable as follows:
(1). They are soluble in 70 wt.% aqueous (i.e., "aq.") glycerine; acetic acid; thioglycolic acid; dichloromethane (i.e., "CH.sub.2 Cl.sub.2 "); trichloromethane (i.e., "CHCl.sub.3 "); salicylaldehyde; dimethylsulfoxide (i.e., "DMSO"); dimethylformamide (i.e., "DMF") and 36 wt.% aq. hydrochloric acid (i.e., "HCl").
(2). They are partially-soluble (meaning that they dissolve hot but tend to precipitate out of solution--or not dissolve therein--when cool) in methanol; ethylene glycol; propanoic acid; crotonaldehyde and p-dioxane. PA1 (3). They are essentially insoluble (meaning very nearly, if not completely, so) in stearic acid; oleic acid; lauric acid; n-butyric acid; ethylene diamine; propylene diamine; diethylene triamine; carbon tetrachloride (i.e., "CCl.sub.4 "); ethylene dichloride (i.e., "C.sub.2 H.sub.4 Cl.sub.2 "); perchloroethylene; chlorothene; acetone; isobutyraldehyde; ether, more specifically diethyl ether (i.e., "(C.sub.2 H.sub.5).sub.2 O"); castor oil; olive oil; cottonseed oil; linseed oil; paraffin oil; methyl-n-amyl ketone; and methyl ethyl ketone. PA1 (4). They are insoluble in ethanol; isopropanol; n-butanol; allyl alcohol; methyallyl alcohol; n-octanol-1; n-decyl alcohol; n-lauryl alcohol; glycerine; diethylene glycol; propylene glycol; tripropylene glycol; 1,3-butylene glycol; monoethanolamine; diethanolamine; and triethanolamine.
The compatibility of K-30 PVO-M with certain salt and other solutions is also meaningful along the above-indicated lines. This is demonstrable by using 1 part by volume (i.e., "vol.pt.") of 10 wt.% aq. PVO-M to which is added the desired aq. (meaning aqueous) solution of salt or other compound until notable turbidity results which indicates the limit of compatibility of the PVO-M with the given solution. Demonstration of this is set forth in the following TABLE II.
TABLE II ______________________________________ COMPATIBILITY OF 10 wt. % aq. PVO--M IN VARIOUS aq. SALT AND OTHER COMPOUND SOLUTIONS Turbidity Point At Given Vol. Pts. Added Solution (With Symbol "#" Indicating No Turb- idity Or Precipitation After Wt. % In aq. Solution Of Charging Of 20 Vol. Pts. Of Particular Added Salt, Etc. Involved Solution) ______________________________________ 1% Ferric Chloride # 50% Calcium Chloride # 20% Ammonium Chloride # 10% HCl # 10% Potassium Alum 0.5 30% Sodium Chloride 1.7 10% Sodium Bicarbonate 0.1 (i.e., "NaHCO.sub.3 ") 10% Sodium Carbonate 0.2 10% Potassium Oxalate 0.3 10% Sodium Hydroxide 0.1 (i.e., "NaOH" or "Caustic (Soda)") 10% Potassium Hydroxide 0.24 (i.e., "KOH" or "Caustic Potash") 0% Methanol # 5% Resorcinol 0.1 5% Tannic Acid 0.1 ______________________________________
As can be seen in TABLE II, the aq. PVO-M solution is compatible with some salts. It is precipitated by strong alkalis and by polyhydroxy compounds. No change with the phenolics appears even upon heating to 110.degree. C. The PVO-M will very readily be precipitated by caustic; a semi-gel viscous mix appearing when only a few drops of 1 M aq. NaOH is added to the WSP solution.
The Formula (II) dimers and higher polymeric forms, including any polymeric (2-ethyl-2-oxazoline), in which the amidocarbonylic unit of the Structure (A) is an integral part of the polymer chain via its amide linkage, are generically representable by: ##STR7## wherein Q is either a polyalkylene unit or merely methylene of the Structure: ##STR8## or, alternatively, an alkyl-substituted unit of the Structure: ##STR9## in which, the same as in R.sub.s is the foregoing Structure (G) for 2-oxazolidinone, the R.sub.s of Structure (T) is a lower alkyl unit containing from 1 to about 6 carbon atoms, such as methyl, ethyl, propyl, etc.; and R" is a substituent containing from 1 to about 10 carbon atoms which can be alkyl; substituted--including substituent alkyl and halo groupings thereon--alkyl, cycloalkyl, including alkyl- and halo-substituted cycloalkysl, and aminoalkyl; and n is an integer with a value of from 2 to 5,000 and in some instances even several thousands higher so as to provide polymer products (when n begins assuming appropriate magnititudes) having Fikentscher K-values (as with PVP, PVO-M and other Formula (I) polymers) in the 1 or 2 to 200 and 200+ range. The Formula (II) polymerizates, as is known, are derived from polymerizable imide oxazoline entities (or monomeric precursors) of the Formula: ##STR10##
When WSP polymerizates of the Formulae (I) and (II) compounds are involved, they are usually homopolymeric in nature, such as PVP and PVO-M. However, they can be utilized in copolymer form as satisfactory WSP's. These, for example, can include copolymers or more than a single species of the Formula (I) or copolymers of more than a single species of the Formula (II-M) or copolymers of one or more of the Formula (I) monomers with one or more of the Formula (II-M) monomers. Copolymeric WSP's can also be comprised of copolymerizates of one or more of the monomeric species of the Formula (I) and/or one or more of the monomeric species of the (II-M) Formula and with other ethylenically (frequently monoethylenically) unsaturated monomers distinct from those of the Formulae (I) which are characterizable in being addition-copolymerizable by known techniques with monomeric N-vinylpyrrolidone and/or monomeric N-vinyl-5-methyl-2-oxazolidinone and/or monomeric precursors for 2-ethyl-2-oxazoline.
In the instances of such diverse WSP copolymers, it is advantageous for the resulting copolymer or multiply-diverse-monomer-containing copolymerizate to be comprised, based on total copolymer weight, of at least about 50 wt.% of at least one Formulae (I) and/or (II-M) monomer; with this more advantageously being at least about 75-80 wt.% of the latter amidocarbonylic group-containing or -providing monomer(s).
Illustrative of such diverse monomers adapted to be copolymerized with Formulae (I) and (II-M) monomerics (including mixtures of one or more thereof) are: 1,3-butadiene; 2,3-dimethyl-1,3-butadiene; isoprene; piperylene; 3-furyl-1,3-butadiene; 3-methyl-1,3-butadiene; chloro-1,3-butadiene; 2-bromo-1,3-butadiene; 2-chloro-3-methyl-1,3-butadiene; styrene; p-chlorostyrene; p-methoxystyrene; alpha-methylstyrene; vinylnaphthalene; acrylic acid; methacrylic acid; methyl acrylate; ethyl acrylate; methyl alpha-chloroacrylate; methyl methacrylate; ethyl methacrylate; butyl methacrylate; methyl ethacrylate; acrylonitrile; methacrylonitrile; methacrylamide; methyl isopropenyl ketone; methyl vinyl ketone; methyl vinyl ether; vinyl-ethinyl alkyl carbinols; vinyl acetate; vinyl chloride; vinylidene chloride; vinylfurane; vinylcarbazole; N-vinyl-3-morpholine; vinyl formate; maleic aced; itaconic acid; fumaric acid; crotonic acid; allyl alcohol; vinyl fluoride; 2-chloroally alcohol; 1-allyloxy-3-chloro-2-propanol; N-vinylsuccinimide; N-tertiarybutyl acrylamide; N-tertiaryoctyl acrylamide; 1,2-dichloropropene-2; 1,2-dichloropropene-1; tri-, tetra- and pentachlorostyrene; o-, m- and p-methyl styrene; p-tertiarybutylstyrene; p-isopropylstyrene; p-phenyl styrene; p-benzoyl styrene; p-cyanostyrene; m-nitrosostyrene; m-trifluoromethylstyrene; m-fluorostyrene; m-tertiarybutyl styrene; stearoylstyrene; olcoylstyrene; linolcylstyrene; alpha-vinylnaphthalene; beta-vinylnaphthalene; 1-(alpha-naphthyl)-propene-1; 2-(alpha-naphthyl)-propene-1; 2-(alpha-naphthyl)-butene-2; 3-(alpha-naphthyl)-pentene-2; 2-bromo-4-trifluoromethylstyrene; beta-bromo-alpha,betadiiodostyrene; beta-bromo-p-methylstyrene; beta-bromo-p-dinitrostyrene; m-secondarybutylstyrene; alpha,beta-dibromostyrene; beta,beta-dibromostyrene; alpha-chloro-2,4,6-trimethylstyrene; alpha-chloro-2,3,4,6-tetramethylstyrene; beta-chloro-o-nitrostyrene; 1chloro-2-(p-tolyl)-1-butene; 4-(1-chlorovinyl)-anisole; 2-(1-chlorovinyl)-4-methylanisole; 1-chloro-4-vinylnaphthylene; 4(1-chlorovinyl)-2-isopropyl-5-methylanisole; 4(2-chlorovinyl)-2-isopropyl-5-methylanisole; p-cyclohexylstyrene; 2-ethyl-1-phenyl-1butene; 3,5-diethyl styrene; 4-fluoro-3-trifluoromethyl-alphamethylstyrene; alpha,alpha-trifluoro-m-propenyltoluene; 2-isopropyl-5-methyl-4-vinyl anisole; 2-methyl-3-phenyl-2-pentene; methyl styryl ether; N,N-dimethyl-m-vinylaniline; 2-(alpha-naphthyl)-2-butene; 1,1-diphenylethylene; propenyl benzene; stilbene; 1-vinylacenaphthene; p-vinylbenzonitrile; p-vinylbiphenyl; 2-vinylfluorene; 6-vinyl-1,2,3,4-tetrahydro-naphthalene; p-vinylphenetole; vinylbutyrate; vinylbenzoate; vinylquinoline; 2-vinylpyridine; 2-methyl-5-vinylpyridine; 4-vinylpyridine; N,N-diallylacrylamide; diallylamine; diallylmethacrylamide; 2,5-dimethyl-3,4-dihydroxy-1,5-hexadiene; 2,5-dimethyl-2,4-hexadiene; divinylbenzene; the divinyl ester of diethylene glycol; trivinylbenzene; 2,7-dimethyl-1,7-octadiene; p-diisopropenylbenzene; 1,3,5-triisopropenylbenzene; p,p'-diisopropenyldiphenyl; 1,1,3,3-tetrallyl-1,3-propanediol; 1,1,3,3-tetramethallyl-1,3-propanediol; 4,6-dimethyl-4,6-dihydroxy-1,8-nonadiene; 2,4,6,8-tetramethyl-4,6-dihydroxy-1,8-nonadiene; nonadiene-1,8; 2,8-dimethylnonadiene -1,8; acetyl triallylcitrate; ethylene; propylene; maleic anhydride; and so forth and so on.
A considerable number of various types and styles of square planar organometallic compounds are known in the art. Good illustrations and representations of these are to be found in Refs. Nos. 23, 25, 29 and 30, especially insofar a concerns those involving platinum as the metallic constituent thereof. They are also nicely illustrated in FIG. 1 of the accompanying Drawing, as the same is explained in the following PARTICULARIZED DESCRIPTION OF THE INVENTION Section of this Specification wherein some known and some novel SPOM's are included. They are also brought forth in connection with Formula (III)/ said Section. The bulk of these, however and insofar as is relevant to anything public known prior to the making of the invention constituting the essence and genesis of the subject matter of the present Application, did not involve ligandal inclusions of aromatic moieties in their structures and none concerned any such SPOM with aromatic ligands with polar substituent group attachments made thereon and affixed thereto.
Complex formations with various complectant and complectate ingredients and combinations are also well known and practiced in the prior art. These, quite frequently, involve phenolic complectates with a variety of complectant substances including, in particular, PVP, PVO-M and the like. Refs. Nos. 1-9, 11-13, 15-17, 19-22 and 26-28 are in one or another way and for one or another purpose germane to this topic.
Thus, it is known that certain substituents on aromatic ring structures, particularly in phenols, are capable of forming stable complexes with polymers that contain the Structure (A) amidocarbonylic moiety. Demonstrative of this, gelatin (a natural protein), polyglycine (a synthetic protein), nylon and PVP have even had rather extensive commercial use to precipitate and isolate from beer the undesired, for one or another reason, tannins, leucoanthocyanins and many other phenolic-type materials and phenols found in the brew as made as the water-insoluble polymer:phenol complex instrumental for the purifying separation.
In further connection with the foregoing BACKGROUND OF THE INVENTION dissertation, the basic principles and limitations of WSP's, SPOM's and various complexes and complex formations are so widely known and comprehended by those skilled in the art that above, and beyond what is here previously set forth, further fundamental expostulation of or elaboration on same is not herein made; the same being unnecessary for thorough understanding and recognition of the advance contributed by and with the instant development and the many benefits obtainable by practice and embodimentations in keeping with the present invention.
Nonetheless, nothing in applicable prior art appears to realistically concern itself with nor suggest, teach, lead to or provide the instantly-contemplated, unique and estimable WSP:SPOM complexes in the way so crucially direct and indigenously advantageous as in the present contribution to the art.